CN101293959A - Hyperbranched conjugated polymer sensing material, preparation method and application thereof - Google Patents
Hyperbranched conjugated polymer sensing material, preparation method and application thereof Download PDFInfo
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- CN101293959A CN101293959A CNA2008100625695A CN200810062569A CN101293959A CN 101293959 A CN101293959 A CN 101293959A CN A2008100625695 A CNA2008100625695 A CN A2008100625695A CN 200810062569 A CN200810062569 A CN 200810062569A CN 101293959 A CN101293959 A CN 101293959A
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- pyridine
- conjugated polymer
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 34
- 239000011540 sensing material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims abstract description 19
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- -1 palladium ions Chemical class 0.000 claims abstract description 12
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 105
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 76
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 72
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 41
- 239000000126 substance Substances 0.000 claims description 40
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 150000001412 amines Chemical class 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 13
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 10
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 10
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000012312 sodium hydride Substances 0.000 claims description 7
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 5
- ZHXUWDPHUQHFOV-UHFFFAOYSA-N 2,5-dibromopyridine Chemical compound BrC1=CC=C(Br)N=C1 ZHXUWDPHUQHFOV-UHFFFAOYSA-N 0.000 claims description 5
- LKPPXSGVBSBIBT-UHFFFAOYSA-N CN(C)C.C#C[Si+3] Chemical compound CN(C)C.C#C[Si+3] LKPPXSGVBSBIBT-UHFFFAOYSA-N 0.000 claims description 5
- NTKVWOTYTNWGRK-UHFFFAOYSA-N P.Br.Br.Br Chemical compound P.Br.Br.Br NTKVWOTYTNWGRK-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229940043279 diisopropylamine Drugs 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- PBIBJSJEDVWZBT-UHFFFAOYSA-N phosphoric acid 1,2,3-trimethylbenzene Chemical compound CC=1C(=C(C=CC1)C)C.P(O)(O)(O)=O PBIBJSJEDVWZBT-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000010025 steaming Methods 0.000 claims description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 claims description 2
- 238000000862 absorption spectrum Methods 0.000 claims description 2
- 238000002189 fluorescence spectrum Methods 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 150000003222 pyridines Chemical class 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 125000004076 pyridyl group Chemical group 0.000 abstract 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000010748 Photoabsorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000004401 flow injection analysis Methods 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 238000003969 polarography Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a hyperbranched conjugated polymer sensing material and a preparation method and an application thereof. According to the invention, triphenylamine is used as a main chain and para-pyridinylene vinylene or para-pyridinylene ethynylene is used as a branch chain, that is, the main chain is introduced with pyridyl groups and ethenylene or ethynylene conjugated thereto, to produce a hyperbranched para-pyridinylene vinylene polymer and a hyperbranched para-pyridinylene ethynylene polymer. The invention realizes the preparation of two hyperbranched fluorescent conjugated polymers through the organic metal catalytic reaction between the raw material of triphenylamine and two pyridine compounds. As a highly sensitive macromolecular fluorescent sensing material, the polymer is used for the detection of palladium ions. Additionally, the polymer has better selectivity to palladium ions than other metal ions.
Description
Technical field
The present invention relates to the chemical sensing material technical field, relate in particular to a kind of hyperbranched conjugated polymer sensing material and its production and use.
Background technology
The identification of alkali and alkaline-earth metal ions, transition metal ion etc. detects and has caused the extensive concern that comprises chemist, biologist, clinical biochemistry man and environmentalist.The analysis test method of palladium mostly is absorption photometry greatly, because this method long reaction time, and sensitivity is lower, so significant limitation is arranged in actual applications.And atomic absorption spectrometry, atomic emissions method, neutron activation, polarography, flow injection spectrophotometry etc., because used instrument is relatively more expensive, so be difficult for promoting the use of.
Fluorescence is a kind of widespread use and the sensing detection means that develop rapidly.Fluorescent optical sensor is that a class can be with the molecule of molecular recognition event by the fluorescent signal effective expression.The fluorescence identification of analytes such as its widespread use and positively charged ion, negatively charged ion and neutral molecule detects.Fluorescence detection has outstanding advantage at aspects such as sensitivity, selectivity and real-time in-situ detections.Thereby, be in recent years more and more noticeable research field to the chemistry and the exploitation of biological substance highly sensitive fluorescent optical sensor.
Conjugated polymers more and more receives publicity in recent ten years as a class sensing material.This is main because some unique photoelectric properties that they demonstrate can obtain various application in photoelectric device making of new generation and the research of chemical-biological fluorescent optical sensor.Conjugated polymers has very strong photo absorption performance, molar extinction coefficient even can be up to 10
6M
-1Cm
-1, and, have the character of " molecular wire ", promptly electronics or excited energy can be on conjugated main chain fast transferring.Quencher molecules only can a small molecules fluorophore of cancellation fluorescence, and quencher molecules combines with any one position on the conjugated polymer chain electronics or transmission ofenergy are obstructed, the fluorescence of cancellation whole piece chain, promptly the fluorescent quenching signal is exaggerated.This " cancellation amplification " effect of conjugated polymers makes it demonstrate response performance rapider, colony with respect to micromolecular fluorescence sense material to the quencher of denier in the surrounding environment.So realization that can be easy is to the nmole even the picomole quantities rapid detection of multiple organic and inorganic and biomolecules.
Hyperbranched polymer had both had the spatial structure characteristic of similar branch-shape polymer, the advantage that has simple synthetic method again, and can optimize respectively by structural unit conduct-nuclear, connection unit and end group and obtain required performance: good solvability, film-forming properties, thermostability and carrier transmission performance.Thereby, obtain significant progress in recent years, become a class new-type functional material.
The present invention is in conjunction with hyperbranched and characteristics conjugated polymers, the synthesis of super branched fluorescent sensing materials made of conjugated polymer, by the pyridine group of introducing in the polymkeric substance, two pyridine units can form coordination compound with the metallic palladium ion in solution, thereby make the fluorescent quenching of conjugated polymers, reach the purpose of detection.By the dissaving structure of conjugated polymers, strengthen " fluorescent quenching amplification " effect simultaneously, improve selectivity and sensitivity the metallic palladium ion detection.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of hyperbranched conjugated polymer sensing material and its production and use is provided.
The hyperbranched conjugated polymer fluorescent sensing material is to be nuclear with the triphenylamine, to pyridine support vinylene or to pyridine support ethynylene is side chain, be to introduce the pyridine group in the main chain and conjugated vinylene or ethynylene obtain hyperbranched to pyridine support vinylene polymkeric substance with hyperbranched pyridine is supportted the ethynylene polymkeric substance with it, wherein, hyperbranched molecular structural formula to pyridine support vinylene polymkeric substance is as follows:
Hyperbranched molecular structural formula to pyridine support ethynylene polymkeric substance is as follows:
Hyperbranched synthetic method to pyridine support vinylene polymkeric substance comprises the steps:
1) 10mol methyltriphenylphospbromide bromide phosphorus is dissolved in 30～50L anhydrous tetrahydro furan, adds 8～12mol alkali under ice bath and argon gas atmosphere, ice bath stirs after 30～50 minutes down, and solution becomes golden yellow; Add 1.5～3mol three (the 4-aldehyde radical phenyl) amine that is dissolved in 100～200mL tetrahydrofuran (THF), remove ice bath, room temperature condition reacted 2～5 days down, added several deionized water termination reactions; Reaction solution is dispersed in methylene dichloride and the water, behind the separatory, organic phase saturated common salt water washing, anhydrous sodium sulfate drying, revolve steaming after, crude product is through column chromatography for separation, vacuum-drying obtains three (4-ethenylphenyl) amine product;
2) with 6mol three (4-ethenylphenyl) amine, 8～10mol 2, the 5-dibromo pyridine, 100～200g palladium, 500～1000g trimethylbenzene phosphoric acid adds in the reactor of anhydrous and oxygen-free, add the anhydrous N of 20～30L, dinethylformamide and 20～30L triethylamine are warmed up to 80～120 ℃ of reactions after 48～72 hours, the reaction solution cool to room temperature, in the impouring methyl alcohol, produce a large amount of scarlet precipitations, filter and collect, be dissolved in the tetrahydrofuran (THF) again, be deposited in the methyl alcohol once more, precipitation is with methyl alcohol extracting 48～72 hours in Soxhlet extractor, and 40～60 ℃ of vacuum-drying 12～48 hours obtains hyperbranched to pyridine support vinylene polymkeric substance.
Described alkali is sodium hydride, potassium tert.-butoxide, sodium tert-butoxide, potassium hydride KH, sodium methylate, sodium ethylate or potassium ethylate.
Hyperbranched synthetic method to pyridine support ethynylene polymkeric substance comprises the steps:
1) with 15.2mol 2,5-dibromo pyridine, 30.8～40mol trimethylammonium ethynyl silicon, 140～190g bi triphenyl phosphorus palladium chloride, 5～10g cuprous iodide, join in the new diethylamine that steams of 50～75L, under the anhydrous and oxygen-free condition, stirring at room 12～24 hours is revolved to steam and is removed diethylamine, is dissolved in 40～60L methyl alcohol, add the alkali aqueous solution of 40～55L 1M, reaction solution stirred 1～2 hour at ambient temperature.Revolve to steam to remove and desolvate, disperse with ether, the saturated common salt water washing, crude product is purified through column chromatography, obtains 2,5-diacetylene pyridine product.
2) with 1mol 2,5-diacetylene pyridine, 0.75～1mol three (4-iodobenzene) amine, 60～90g bi triphenyl phosphorus palladium chloride, 10～15g cuprous iodide, join in the anhydrous Diisopropylamine mixed solvent of 20～40L dry toluene and 10～20L, under the anhydrous and oxygen-free condition, 70～85 ℃ were stirred 48～72 hours, reaction solution cool to room temperature then, in the impouring methyl alcohol, obtain the scarlet polymkeric substance after the stirred for several hour, filter and collect, be dissolved in the tetrahydrofuran (THF) again, be deposited in the methyl alcohol once more, precipitation is with methyl alcohol extracting 48～72 hours in Soxhlet extractor, and 40～60 ℃ of vacuum-drying 12～24 hours obtains hyperbranched to pyridine support ethynylene polymkeric substance.
Described alkali aqueous solution is potassium hydroxide, sodium hydride, sodium hydroxide or salt of wormwood.
Hyperbranched conjugated polymer is used for palladium ion and detects.
The method that hyperbranched conjugated polymer is used for the palladium ion detection comprises the steps:
1) with solvent hyperbranched conjugated polymer is made into 10
-4～10
-6The hyperbranched conjugated polymer dilute solution of mol/L;
2) test substance is configured to 10
-2～10
-3The solution of mol/L joins in the hyperbranched conjugated polymer dilute solution then, measures ultra-violet absorption spectrum and fluorescence emission spectrum, according to the variation of fluorescence intensity, determines palladium ion content.
The present invention is raw material with the triphenylamine, carries out the organo-metallic catalyzed reaction with other two kinds of pyridine compounds, has synthesized two kinds of hyperbranched fluorescent conjugated polymers.This polymkeric substance is the highly sensitive high molecular fluorescent sensing material of a class, is used for the detection to palladium ion.In addition, this polymer phase has selectivity preferably for other metal ion to palladium ion.
Description of drawings
Fig. 1 is that synthetic is hyperbranched to the fluorescent emission spectrogram of pyridine support vinylene polymkeric substance under the situation that different concns palladium metal ion exists among the present invention, and excitation wavelength is 405nm;
Fig. 2 is that the synthetic hyperbranched conjugated polymer is adding different metal ionic concentration respectively to 15*10 among the present invention
-6During M, to the cancellation effect contrast figure of polymer fluorescent emission.
Embodiment
Content for a better understanding of the present invention further specifies technical scheme of the present invention below by specific embodiment.
Embodiment 1, hyperbranched preparation to pyridine support vinylene polymkeric substance
1) 10mol methyltriphenylphospbromide bromide phosphorus is dissolved in the 30L anhydrous tetrahydro furan, adds the 8mol sodium hydride under ice bath and argon gas atmosphere, ice bath stirs after 30 minutes down, and solution becomes golden yellow; Add 1.5mol three (the 4-aldehyde radical phenyl) amine that is dissolved in the 100mL tetrahydrofuran (THF), remove ice bath, room temperature condition reacted 2 days down, added several deionized water termination reactions; Reaction solution is dispersed in methylene dichloride and the water, behind the separatory, organic phase saturated common salt water washing, anhydrous sodium sulfate drying, revolve steaming after, crude product is through column chromatography for separation, vacuum-drying, obtain three (4-ethenylphenyl) amine product (
1H NMR (CDCl
3, δ ppm): 7.3 (d, 6H), 7.06 (d, 6H), 6.96 (m, 3H), 5.69 (d, 3H), 5.19 (d, 3H);
13C NMR (CDCl
3, δ ppm): 147.1,136.3,132.5,127.3,124.2,112.6; Elemental analysis:Anal.calcd. (%) for C
24H
21N:C, 89.12; H, 6.54; N, 4.33.Found:C, 89.23; H, 6.48; N, 4.29);
2) with 6mol three (4-ethenylphenyl) amine, 8mol 2, the 5-dibromo pyridine, the 100g palladium, 500g trimethylbenzene phosphoric acid adds in the reactor of anhydrous and oxygen-free, add the anhydrous N of 20L, dinethylformamide and 20L triethylamine are warmed up to 80 ℃ of reactions after 48 hours, the reaction solution cool to room temperature, in the impouring methyl alcohol, produce a large amount of scarlet precipitations, filter and collect, be dissolved in the tetrahydrofuran (THF) again, be deposited in the methyl alcohol once more, precipitation is with methyl alcohol extracting 48 hours in Soxhlet extractor, 40 ℃ of vacuum-drying 12 hours, obtain hyperbranched to pyridine support vinylene polymkeric substance (
1H NMR (CDCl
3, δ ppm): 9.27,8.27,8.00,7.67,7.47-6.92,6.66,5.65,5.16; FTIR (KBr pellet, cm
-1): 3032,1595,1504,1322,1092,833).
Embodiment 2, hyperbranched preparation to pyridine support vinylene polymkeric substance
1) 10mol methyltriphenylphospbromide bromide phosphorus is dissolved in the 50L anhydrous tetrahydro furan, adds the 12mol sodium hydride under ice bath and argon gas atmosphere, ice bath stirs after 50 minutes down, and solution becomes golden yellow; Add 3mol three (the 4-aldehyde radical phenyl) amine that is dissolved in the 200mL tetrahydrofuran (THF), remove ice bath, room temperature condition reacted 2～5 days down, added several deionized water termination reactions; Reaction solution is dispersed in methylene dichloride and the water, behind the separatory, organic phase saturated common salt water washing, anhydrous sodium sulfate drying, revolve steaming after, crude product is through column chromatography for separation, vacuum-drying obtains three (4-ethenylphenyl) amine product;
2) with 6mol three (4-ethenylphenyl) amine, 10mol 2, the 5-dibromo pyridine, the 200g palladium, 1000g trimethylbenzene phosphoric acid adds in the reactor of anhydrous and oxygen-free, add the anhydrous N of 30L, dinethylformamide and 30L triethylamine are warmed up to 120 ℃ of reactions after 72 hours, the reaction solution cool to room temperature, in the impouring methyl alcohol, produce a large amount of scarlet precipitations, filter and collect, be dissolved in the tetrahydrofuran (THF) again, be deposited in the methyl alcohol once more, precipitation is with methyl alcohol extracting 72 hours in Soxhlet extractor, and 60 ℃ of vacuum-drying 48 hours obtains hyperbranched to pyridine support vinylene polymkeric substance.
Embodiment 3, hyperbranched preparation to pyridine support vinylene polymkeric substance
1) 10mol methyltriphenylphospbromide bromide phosphorus is dissolved in the 30L anhydrous tetrahydro furan, adds the 9mol sodium hydride under ice bath and argon gas atmosphere, ice bath stirs after 30 minutes down, and solution becomes golden yellow; Add 2.1mol three (the 4-aldehyde radical phenyl) amine that is dissolved in the 150mL tetrahydrofuran (THF), remove ice bath, room temperature condition reacted 3 days down, added several deionized water termination reactions; Reaction solution is dispersed in methylene dichloride and the water, behind the separatory, organic phase saturated common salt water washing, anhydrous sodium sulfate drying, revolve steaming after, crude product is through column chromatography for separation, vacuum-drying obtains three (4-ethenylphenyl) amine product;
2) with 6mol three (4-ethenylphenyl) amine, 9mol 2, the 5-dibromo pyridine, the 150g palladium, 750g trimethylbenzene phosphoric acid adds in the reactor of anhydrous and oxygen-free, add the anhydrous N of 25L, dinethylformamide and 25L triethylamine are warmed up to 90 ℃ of reactions after 48 hours, the reaction solution cool to room temperature, in the impouring methyl alcohol, produce a large amount of scarlet precipitations, filter and collect, be dissolved in the tetrahydrofuran (THF) again, be deposited in the methyl alcohol once more, precipitation is with methyl alcohol extracting 48 hours in Soxhlet extractor, and 60 ℃ of vacuum-drying 12 hours obtains hyperbranched to pyridine support vinylene polymkeric substance.
Embodiment 4, hyperbranched preparation to pyridine support ethynylene polymkeric substance
1) with 15.2mol 2,5-dibromo pyridine, 30.8mol trimethylammonium ethynyl silicon, 140g bi triphenyl phosphorus palladium chloride, 5g cuprous iodide, join in the new diethylamine that steams of 50L, under the anhydrous and oxygen-free condition, stirring at room 12 hours is revolved to steam and is removed diethylamine, is dissolved in the 40L methyl alcohol, add the potassium hydroxide aqueous solution of 40L 1M, reaction solution stirred 1 hour at ambient temperature.Revolve to steam to remove and desolvate, disperse with ether, the saturated common salt water washing, crude product is purified through column chromatography, obtains 2,5-diacetylene pyridine product (
1H NMR (CDCl
3, δ ppm): 8.64 (s, 1H), 7.70 (d, 1H), 7.41 (d, 1H), 3.28 (s, 1H), 3.23 (s, 1H);
13C NMR (CDCl
3, δ ppm): 152.9,141.5,139.1,126.6,119.0,82.4,82.3,79.9,79.0; Elementalanalysis:Anal.calcd. (%) for C
9H
5N:C, 85.02; H, 3.96; N, 11.02.Found:C, 84.72; H, 4.01; N, 10.93);
2) with 1mol 2,5-diacetylene pyridine, three 0.75mol (4-iodobenzene) amine, 60g bi triphenyl phosphorus palladium chloride, the 10g cuprous iodide, join in the anhydrous Diisopropylamine mixed solvent of 20L dry toluene and 10L, under the anhydrous and oxygen-free condition, 70 ℃ were stirred 48 hours, reaction solution cool to room temperature then, in the impouring methyl alcohol, obtain the scarlet polymkeric substance after the stirred for several hour, filter and collect, be dissolved in the tetrahydrofuran (THF) again, be deposited in the methyl alcohol once more, precipitation is with methyl alcohol extracting 48 hours in Soxhlet extractor, 40 ℃ of vacuum-drying 12 hours, obtain hyperbranched to pyridine support ethynylene product polymkeric substance (
1H NMR (CDCl
3, δ ppm): 8.73,7.76-7.29,7.01,6.85,3.72; FTIR (KBr pellet, cm
-1): 2965,2212,1581,1482,1316,1097,816).
1) with 15.2mol 2,5-dibromo pyridine, 40mol trimethylammonium ethynyl silicon, 190g bi triphenyl phosphorus palladium chloride, 10g cuprous iodide, join in the new diethylamine that steams of 75L, under the anhydrous and oxygen-free condition, stirring at room 24 hours is revolved to steam and is removed diethylamine, is dissolved in the 60L methyl alcohol, add the potassium hydroxide aqueous solution of 55L 1M, reaction solution stirred 2 hours at ambient temperature.Revolve to steam to remove and desolvate, disperse with ether, the saturated common salt water washing, crude product is purified through column chromatography, obtains 2,5-diacetylene pyridine product;
2) with 1mol 2,5-diacetylene pyridine, 1mol three (4-iodobenzene) amine, 90g bi triphenyl phosphorus palladium chloride, the 15g cuprous iodide, join in the anhydrous Diisopropylamine mixed solvent of 40L dry toluene and 20L, under the anhydrous and oxygen-free condition, 85 ℃ were stirred 72 hours, reaction solution cool to room temperature then, in the impouring methyl alcohol, obtain the scarlet polymkeric substance after the stirred for several hour, filter and collect, be dissolved in the tetrahydrofuran (THF) again, be deposited in the methyl alcohol once more, precipitation is with methyl alcohol extracting 72 hours in Soxhlet extractor, and 60 ℃ of vacuum-drying 24 hours obtains hyperbranched to pyridine support ethynylene product polymkeric substance.
Embodiment 6, hyperbranched preparation to pyridine support ethynylene polymkeric substance
1) with 15.2mol 2,5-dibromo pyridine, 35mol trimethylammonium ethynyl silicon, 160g bi triphenyl phosphorus palladium chloride, 7g cuprous iodide, join in the new diethylamine that steams of 60L, under the anhydrous and oxygen-free condition, stirring at room 12 hours is revolved to steam and is removed diethylamine, is dissolved in the 50L methyl alcohol, add the potassium hydroxide aqueous solution of 50L 1M, reaction solution stirred 1.5 hours at ambient temperature.Revolve to steam to remove and desolvate, disperse with ether, the saturated common salt water washing, crude product is purified through column chromatography, obtains 2,5-diacetylene pyridine product;
2) with 1mol 2,5-diacetylene pyridine, three 0.8mol (4-iodobenzene) amine, 75g bi triphenyl phosphorus palladium chloride, the 12g cuprous iodide, join in the anhydrous Diisopropylamine mixed solvent of 30L dry toluene and 15L, under the anhydrous and oxygen-free condition, 75 ℃ were stirred 48 hours, reaction solution cool to room temperature then, in the impouring methyl alcohol, obtain the scarlet polymkeric substance after the stirred for several hour, filter and collect, be dissolved in the tetrahydrofuran (THF) again, be deposited in the methyl alcohol once more, precipitation is with methyl alcohol extracting 48 hours in Soxhlet extractor, and 60 ℃ of vacuum-drying 12 hours obtains hyperbranched to pyridine support ethynylene product polymkeric substance.
The detection of palladium ion
Polymkeric substance is made into 1*10
-6The tetrahydrofuran solution of M adds the palladium metal ion solution in system.Increase palladium metal ionic concentration gradually, ultrasonic 10 minutes of each adding back is observed by fluorescence spectrophotometer, finds that the fluorescence of polymkeric substance has tangible quenching phenomenon when palladium ion concentration is less.By comparing with the cancellation effect of other metal ion, can obtain this base polymer has selectivity preferably to palladium ion.Therefore, prove that this base polymer can effectively detect the palladium metal ion.
Claims (7)
1, a kind of hyperbranched conjugated polymer fluorescent sensing material, it is characterized in that with the triphenylamine being nuclear, to pyridine support vinylene or to pyridine support ethynylene is side chain, be to introduce the pyridine group in the main chain and conjugated vinylene or ethynylene obtain hyperbranched to pyridine support vinylene polymkeric substance with hyperbranched pyridine is supportted the ethynylene polymkeric substance with it, wherein, hyperbranched molecular structural formula to pyridine support vinylene polymkeric substance is as follows:
Hyperbranched molecular structural formula to pyridine support ethynylene polymkeric substance is as follows:
2, a kind of preparation method of hyperbranched conjugated polymer fluorescent sensing material as claimed in claim 1 is characterized in that comprising the steps:
1) 10mol methyltriphenylphospbromide bromide phosphorus is dissolved in 30～50L anhydrous tetrahydro furan, adds 8～12mol alkali under ice bath and argon gas atmosphere, ice bath stirs after 30～50 minutes down, and solution becomes golden yellow; Add 1.5～3mol three (the 4-aldehyde radical phenyl) amine that is dissolved in 100～200mL tetrahydrofuran (THF), remove ice bath, room temperature condition reacted 2～5 days down, added several deionized water termination reactions; Reaction solution is dispersed in methylene dichloride and the water, behind the separatory, organic phase saturated common salt water washing, anhydrous sodium sulfate drying, revolve steaming after, crude product is through column chromatography for separation, vacuum-drying obtains three (4-ethenylphenyl) amine product;
2) with 6mol three (4-ethenylphenyl) amine, 8～10mol 2, the 5-dibromo pyridine, 100～200g palladium, 500～1000g trimethylbenzene phosphoric acid adds in the reactor of anhydrous and oxygen-free, add the anhydrous N of 20～30L, dinethylformamide and 20～30L triethylamine are warmed up to 80～120 ℃ of reactions after 48～72 hours, the reaction solution cool to room temperature, in the impouring methyl alcohol, produce a large amount of scarlet precipitations, filter and collect, be dissolved in the tetrahydrofuran (THF) again, be deposited in the methyl alcohol once more, precipitation is with methyl alcohol extracting 48～72 hours in Soxhlet extractor, and 40～60 ℃ of vacuum-drying 12～48 hours obtains hyperbranched to pyridine support vinylene polymkeric substance.
3, the preparation method of a kind of hyperbranched conjugated polymer fluorescent sensing material according to claim 2 is characterized in that described alkali is sodium hydride, potassium tert.-butoxide, sodium tert-butoxide, potassium hydride KH, sodium methylate, sodium ethylate or potassium ethylate.
4, a kind of preparation method of hyperbranched conjugated polymer fluorescent sensing material as claimed in claim 1 is characterized in that comprising the steps:
1) with 15.2mol 2,5-dibromo pyridine, 30.8～40mol trimethylammonium ethynyl silicon, 140～190g bi triphenyl phosphorus palladium chloride, 5～10g cuprous iodide, join in the new diethylamine that steams of 50～75L, under the anhydrous and oxygen-free condition, stirring at room 12～24 hours is revolved to steam and is removed diethylamine, is dissolved in 40～60L methyl alcohol, add the alkali aqueous solution of 40～55L 1M, reaction solution stirred 1～2 hour at ambient temperature.Revolve to steam to remove and desolvate, disperse with ether, the saturated common salt water washing, crude product is purified through column chromatography, obtains 2,5-diacetylene pyridine product.
2) with 1mol 2,5-diacetylene pyridine, 0.75～1mol three (4-iodobenzene) amine, 60～90g bi triphenyl phosphorus palladium chloride, 10～15g cuprous iodide, join in the anhydrous Diisopropylamine mixed solvent of 20～40L dry toluene and 10～20L, under the anhydrous and oxygen-free condition, 70～85 ℃ were stirred 48～72 hours, reaction solution cool to room temperature then, in the impouring methyl alcohol, obtain the scarlet polymkeric substance after the stirred for several hour, filter and collect, be dissolved in the tetrahydrofuran (THF) again, be deposited in the methyl alcohol once more, precipitation is with methyl alcohol extracting 48～72 hours in Soxhlet extractor, and 40～60 ℃ of vacuum-drying 12～24 hours obtains hyperbranched to pyridine support ethynylene polymkeric substance.
5, the preparation method of a kind of hyperbranched conjugated polymer fluorescent sensing material according to claim 3 is characterized in that described alkali aqueous solution is potassium hydroxide, sodium hydride, sodium hydroxide or salt of wormwood.
6, a kind of purposes of hyperbranched conjugated polymer fluorescent sensing material as claimed in claim 1 is characterized in that hyperbranched conjugated polymer is used for palladium ion and detects.
7, the purposes of a kind of hyperbranched conjugated polymer fluorescent sensing material according to claim 6 is characterized in that described hyperbranched conjugated polymer is used for the method that palladium ion detects and comprises the steps:
1) with solvent hyperbranched conjugated polymer is made into 10
-4～10
-6The hyperbranched conjugated polymer dilute solution of mol/L;
2) test substance is configured to 10
-2～10
-3The solution of mol/L joins in the hyperbranched conjugated polymer dilute solution then, measures ultra-violet absorption spectrum and fluorescence emission spectrum, according to the variation of fluorescence intensity, determines palladium ion content.
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| CN106770080A (en) * | 2016-11-15 | 2017-05-31 | 山西大学 | A kind of Pd2+Detection reagent and its synthetic method and application |
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| CN106770080A (en) * | 2016-11-15 | 2017-05-31 | 山西大学 | A kind of Pd2+Detection reagent and its synthetic method and application |
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